Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations
Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations
复制标题
将吩噻嗪组装到多孔配位笼中以提高其有机转化的光催化效率
DOI：
10.1002/anie.202214055
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Bose, Riya
中科院分区：
文献类型：
--
作者：
Lin, Hengyu;Xiao, Zhifeng;Le, Khoa N.;Yan, Tian‐hao;Cai, Peiyu;Yang, Yihao;Day, Gregory S.;Drake, Hannah F.;Xie, Haomiao;Bose, Riya
小分子光催化通常受到催化剂降解和低电子转移效率的限制。本文报道了一种稳定的N -苯基-吩噻嗪（PTH）衍生的多孔配位笼（PCC）作为高效光催化剂。通过将光催化PTH片段掺入PCC，可以降低聚集诱导猝灭（AIQ）。催化剂稳定性的改善被发现，归因于PTH部分的协同作用。该催化剂通过光解单电子转移作用，用于光催化脱卤和硼化反应。对硼化反应的催化机理进行了评价，结果表明，硼化反应性能的提高是由于电子供体-受体（EDA）配合物与笼更有效地形成。这一发现为通过超分子化学改善小分子有机光催化剂的光物理性质和稳定性提供了一种潜在的策略。
Photo‐catalysis by small‐molecules is often limited by catalyst degradation and low electron‐transfer efficiency. Herein we report a stable N‐phenyl‐phenothiazine (PTH)‐derived porous coordination cage (PCC) as a highly efficient photocatalyst. By the incorporation of the photocatalytic PTH moiety into a PCC, aggregation‐induced quenching (AIQ) was shown to be reduced. An improvement in catalyst stability was discovered, ascribed to the synergistic effects of the PTH moieties. The catalyst, operating through a photolytic single‐electron transfer, was utilized for photo‐catalyzed dehalogenation and borylation. Evaluation of the catalytic mechanism in the borylation reaction showed that the improved performance results from the more efficient formation of the electron donor‐acceptor (EDA) complex with the cage. This discovery provides a potential strategy to improve the photophysical properties and stabilities of small‐molecule organic photocatalysts via supramolecular chemistry.